US5068453A - Novel monoterpenes - Google Patents
Novel monoterpenes Download PDFInfo
- Publication number
- US5068453A US5068453A US07/491,459 US49145990A US5068453A US 5068453 A US5068453 A US 5068453A US 49145990 A US49145990 A US 49145990A US 5068453 A US5068453 A US 5068453A
- Authority
- US
- United States
- Prior art keywords
- monoterpenes
- acaridial
- acarids
- isolated
- nmr
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229930003658 monoterpene Natural products 0.000 title claims abstract description 18
- 150000002773 monoterpene derivatives Chemical class 0.000 title claims abstract description 18
- 235000002577 monoterpenes Nutrition 0.000 title claims abstract description 18
- 241000894006 Bacteria Species 0.000 abstract description 6
- 239000003205 fragrance Substances 0.000 abstract description 4
- 239000000877 Sex Attractant Substances 0.000 abstract description 3
- 230000006378 damage Effects 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 208000027418 Wounds and injury Diseases 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 208000014674 injury Diseases 0.000 abstract description 2
- 125000001412 tetrahydropyranyl group Chemical group 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- WFMDNHSSEXHQAN-BJMVGYQFSA-N (2e)-2-(4-methylpent-3-enylidene)butanedial Chemical compound CC(C)=CC\C=C(C=O)/CC=O WFMDNHSSEXHQAN-BJMVGYQFSA-N 0.000 description 9
- WFMDNHSSEXHQAN-UHFFFAOYSA-N Beta-Acaridial Natural products CC(C)=CCC=C(C=O)CC=O WFMDNHSSEXHQAN-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- RZUYNBNUYOKGPO-UHFFFAOYSA-N 2-(4-methylpent-3-enyl)but-2-enedial Chemical compound CC(C)=CCCC(C=O)=CC=O RZUYNBNUYOKGPO-UHFFFAOYSA-N 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- RZUYNBNUYOKGPO-UXBLZVDNSA-N (e)-2-(4-methylpent-3-enyl)but-2-enedial Chemical compound CC(C)=CCC\C(C=O)=C/C=O RZUYNBNUYOKGPO-UXBLZVDNSA-N 0.000 description 5
- 241000333978 Caloglyphus Species 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- GIABTDUEDSBLGQ-POHAHGRESA-N (z)-2-(4-methylpent-3-enyl)but-2-ene-1,4-diol Chemical compound CC(C)=CCC\C(CO)=C\CO GIABTDUEDSBLGQ-POHAHGRESA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 241000132125 Tyrophagus Species 0.000 description 2
- 241000611866 Tyrophagus putrescentiae Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- GIABTDUEDSBLGQ-UHFFFAOYSA-N (Z)-2-(4-Methyl-3-pentenyl)-2-butene-1,4-diol Natural products CC(C)=CCCC(CO)=CCO GIABTDUEDSBLGQ-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 241000223602 Alternaria alternata Species 0.000 description 1
- 241000223221 Fusarium oxysporum Species 0.000 description 1
- 241000228143 Penicillium Species 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000005667 attractant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000031902 chemoattractant activity Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N49/00—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds containing the group, wherein m+n>=1, both X together may also mean —Y— or a direct carbon-to-carbon bond, and the carbon atoms marked with an asterisk are not part of any ring system other than that which may be formed by the atoms X, the carbon atoms in square brackets being part of any acyclic or cyclic structure, or the group, wherein A means a carbon atom or Y, n>=0, and not more than one of these carbon atoms being a member of the same ring system, e.g. juvenile insect hormones or mimics thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
- C07C33/025—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond
- C07C33/035—Alkenediols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
- C07C45/305—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation with halogenochromate reagents, e.g. pyridinium chlorochromate
Definitions
- the present invention relates to novel monoterpenes.
- Monoterpenes are hydrocarbons having a basal structure of C 10 H 16 . Most of them are naturally found in essential oils. The monoterpenes have been utilized, for example, in an insecticide, medicine or perfume due to their volatility and fragrance.
- Novel monoterpenes have been isolated from agriculturally harmful acarids and then identified. They have fragrance of citrus-note and are bactericidally active against bacteria which may cause crop injury. Some of them are the first sex pheromones to be isolated from the acarids.
- the present invention provides monoterpenes of the formulae: ##STR2## wherein X, Y and Y' are independently --CHO, --CO 2 H or --CH 2 OR, R being hydrogen or tetrahydropyranyl, and Y may be in E- or Z-form about the adjacent double bond.
- the monoterpenes of the formula (I) can be obtained from an acarid named Tyrophagus perniciosus.
- acarids such as Tyrophagus putrescentiae and Caloglyphus polyphyllae give the monoterpenes of the formula (II).
- the present monoterpenes (I) and (II) have fragrance of citrus-note and bactericidal activity against some bacteria which may harm crops.
- the monoterpenes (II) are the first sex pheromones that have been isolated from genus acarid, which attract male Caloglyphus polyphyllae. Therefore, it is possible to use the monoterpenes (II) as an attractant.
- the present monoterpenes can be obtained as follows by the isolation from the acarids or the synthesis:
- Tyrophagus perniciosus was cultured and extracted with n-hexane.
- the extract was subjected to silica column chromatography eluted with n-hexane/ether. ⁇ -Acaridial was obtained in fractions of 95:5-90:10.
- ⁇ -acaridial was isolated from Tyrophagus putrescentiae in the fractions of 90:10-80:20.
- the present monoterpenes (I) can be obtained according to the following reaction formulae: ##STR8##
- a usual agar medium was used as a culture medium for the bacteria.
- a solution of the test compound in ethanol was applied on the disc so as to inhibit the bacteria.
- the bactericidal activity was determined as a diameter of the inhibited area.
- the positive attraction was achieved with the minimal concentration of ⁇ -acaridial of 1 ppm, which is about a half of the ⁇ -acaridial concentration in one head of female Caloglyphus polyphyllae.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Insects & Arthropods (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
Monoterpenes of the formulae: <IMAGE> (I) and <IMAGE> (II) wherein X, Y and Y' are independently -CHO, -CO2H or -CH2OR, R being hydrogen or tetrahydropyranyl, and Y may be in E- or Z-form about the adjacent double bond have been isolated from agriculturally harmful acarids and then identified. They have fragrance of citrus-note and are bactericidally active against bacteria which may cause crop injury. Some of them are the first sex pheromones to be isolated from the acarids.
Description
Field of the Invention
The present invention relates to novel monoterpenes.
Description of the Related Art
Monoterpenes are hydrocarbons having a basal structure of C10 H16. Most of them are naturally found in essential oils. The monoterpenes have been utilized, for example, in an insecticide, medicine or perfume due to their volatility and fragrance.
Novel monoterpenes have been isolated from agriculturally harmful acarids and then identified. They have fragrance of citrus-note and are bactericidally active against bacteria which may cause crop injury. Some of them are the first sex pheromones to be isolated from the acarids.
Accordingly, the present invention provides monoterpenes of the formulae: ##STR2## wherein X, Y and Y' are independently --CHO, --CO2 H or --CH2 OR, R being hydrogen or tetrahydropyranyl, and Y may be in E- or Z-form about the adjacent double bond.
The monoterpenes of the formula (I) can be obtained from an acarid named Tyrophagus perniciosus.
Other acarids such as Tyrophagus putrescentiae and Caloglyphus polyphyllae give the monoterpenes of the formula (II).
The present monoterpenes (I) and (II) have fragrance of citrus-note and bactericidal activity against some bacteria which may harm crops.
In addition, the monoterpenes (II) are the first sex pheromones that have been isolated from genus acarid, which attract male Caloglyphus polyphyllae. Therefore, it is possible to use the monoterpenes (II) as an attractant.
Specific examples of the present monoterpenes as well as their characteristic data are shown as follows:
2-(4-methyl-3-pentenyl)-2-butenedial (hereinafter referred to as α-acaridial): ##STR3##
MS: 166.0983 (M+)
IR (CCl4): 1690 cm-1
UV (hexane): λmax =240 nm, ε=23500
NMR (500 MHz, CDCl3): δ=9.67 (s), 10.17 (d, J=7.54 Hz), 6.51 (d, J=7.54 Hz), 5.07 (triplet-quintet, J=7.74, 7.64, 1.5 ppm), 2.71 (t, J=7.14 Hz), 2.19 (q, J=7.4 Hz), 1.65 (3H, s), 1.50 (2H, s).
2-(4-methyl-3-pentenyl)-2(E)-butenediol [hereinafter referred to as α-(E)-acaridiol]: ##STR4##
NMR (500 MHz, CDCl3) δ=5.69 (1H, t, J=6.85 Hz), 5.11 (1H, m), 4.21 (2H, d, J=6.85 Hz), 4.09 (2H, s), 2.05-2.20 (4H, m), 1.69 (3H, s), 1.61 (3H, s).
13 C-NMR: δ=142.34, 132.76, 124.72, 123.57, 66.38, 58.88, 28.24, 27.19, 25.68, 17.75.
2-(4-methyl-3-pentenyl)-2(Z)-butenediol [hereinafter referred to as α-(Z)-acaridiol]: ##STR5##
NMR (500 MHz, CDCl3): δ=5.64 (1H, t, J=6.87 Hz), 5.11 (1H, m), 4.21 (2H, d, J=6.87), 4.18 (2H, s), 2.02-2.20 (4H, m), 1.69 (3H, s), 1.61 (3H, s).
13 C-NMR: δ=143.71, 132.22, 126.75, 123.68, 61.05, 58.83, 35.82, 26.71, 25.68, 17.75.
2(E)-(4-methyl-3-pentenylidene)-butanedial (hereinafter referred to as β-acaridial): ##STR6##
MS: 166.0988 (M+), M/Z =151, 137, 123
IR (CCl4): 2810, 2700, 1720, 1680 cm-1
UV (hexane): λmax =225 nm, ε=13600
NMR (500 MHz, CDCl3): δ=9.45 (s), 9.62 (t, J=1.6 Hz), 6.75 (t, J=7.44 Hz), 5.12 (triplet-quintet, J=7.25, 7.1, 1.28 Hz), 3.43 (2H, d, J=1.3 Hz), 3.00 (2H, t, J=7.34 Hz), 1.73 (3H, s), 1.65 (3H, s).
2(E)-(4-methyl-3-pentenylidene)-butanediol (hereinafter referred to as β-acaridiol): ##STR7##
13 C-NMR: δ=135.97 (C), 132.47 (C), 130.02 (CH), 121.99 (CH), 61.80 (CH2), 58.45 (CH2), 32.38 (CH2), 26.82 (CH2), 25.67 (CH3), 17.77 (CH3).
The present monoterpenes can be obtained as follows by the isolation from the acarids or the synthesis:
Isolation from acarids:
Tyrophagus perniciosus was cultured and extracted with n-hexane. The extract was subjected to silica column chromatography eluted with n-hexane/ether. α-Acaridial was obtained in fractions of 95:5-90:10.
By the same way, β-acaridial was isolated from Tyrophagus putrescentiae in the fractions of 90:10-80:20.
Synthesis:
The present monoterpenes (I) can be obtained according to the following reaction formulae: ##STR8##
Bactericidal activity of α-acaridial and β-acaridial
By using a paper disc for antibiotics assay (diameter: 8 cm), the bactericidal activity of α-acaridial and β-acaridial was examined against the bacteria shown in Tables 1 and 2.
In the examination, a usual agar medium was used as a culture medium for the bacteria. A solution of the test compound in ethanol was applied on the disc so as to inhibit the bacteria. The bactericidal activity was determined as a diameter of the inhibited area.
The results as well as the concentration of the ethanol solution of the test compounds are shown in Tables 1 and 2.
TABLE 1
______________________________________
Bactericidal activity of α-acaridial
Concentration
Inhibition diameter (mm)
(μm/ml) A P F
______________________________________
1000 9 15.8 13.6
500 8 13.6 11.7
250 -- 12.0 10.1
125 -- 10.3 8.5
______________________________________
TABLE 2
______________________________________
Bactericidal activity of β-acaridial
Concentration
Inhibition diameter (mm)
(μm/ml) A P F
______________________________________
500 8.0 14.3 11.5
400 -- 12.0 10.3
320 -- 11.6 9.7
256 -- 11.1 9.5
205 -- 11.1 8.8
164 -- 9.6 8.6
131 -- 9.4 8.4
105 -- 9.3 8.0
84 -- 8.0 --
______________________________________
A: Alternaria alternata
P: Penicillium Vermicalatum IFO 7231
F: Fusarium Oxysporum
Attraction of β-acaridial for male Caloglyphus polyphyllae
Into a dish (diameter: 4 cm) containing a small amount of dry yeast on the center thereof and a moist piece of filter paper placed aside from the center, ten head of male Caloglyphus polyphyllae were introduced. The moment the acarids began to eat the yeast, two pieces of filter paper were put on the dish symmetrically about the center, one piece containing a solution of the test compound and the other piece only a solvent as a control. The distance between the center of the dish and each piece was 1 cm. The attraction was concluded to be positive when the acarid stopped to eat and moved or were headed toward the test piece.
The positive attraction was achieved with the minimal concentration of β-acaridial of 1 ppm, which is about a half of the β-acaridial concentration in one head of female Caloglyphus polyphyllae.
Claims (3)
1. A monoterpene of the formula: ##STR9##
2. A monoterpene of the formula: ##STR10##
3. A monoterpene of the formula: ##STR11##
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-60324 | 1989-03-13 | ||
| JP6032489A JPH02240033A (en) | 1989-03-13 | 1989-03-13 | New monoterpenes and their derivatives |
| JP10993889A JPH02286640A (en) | 1989-04-28 | 1989-04-28 | New monoterpenes and their derivatives |
| JP1-109938 | 1989-04-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5068453A true US5068453A (en) | 1991-11-26 |
Family
ID=26401397
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/491,459 Expired - Lifetime US5068453A (en) | 1989-03-13 | 1990-03-09 | Novel monoterpenes |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US5068453A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6214888B1 (en) | 1996-09-18 | 2001-04-10 | Applied Genetics Incorporated | Dermatological compounds |
| US6623724B2 (en) | 1996-09-18 | 2003-09-23 | Applied Genetics Incorporated Dermatics | Dermatological compositions and methods |
| EP1420640A4 (en) * | 2001-08-28 | 2004-11-24 | Eden Research Plc | Treatment and prevention of infections in plants |
| US20060127944A1 (en) * | 2002-04-30 | 2006-06-15 | Renthal Robert D | Method for pheromone discovery in insects |
| US20080220038A1 (en) * | 2004-01-23 | 2008-09-11 | Lanny Franklin | Nematicidal Compositions and Methods of Using Them |
| US20100040656A1 (en) * | 2004-05-20 | 2010-02-18 | Lanny Franklin | Compositions containing a hollow glucan particle or a cell wall particle encapsulating a terpene component, methods of making and using them |
| US9439416B2 (en) | 2005-11-30 | 2016-09-13 | Eden Research Plc | Compositions and methods comprising terpenes or terpene mixtures selected from thymol, eugenol, geraniol, citral, and l-carvone |
| US10383329B2 (en) | 2012-11-21 | 2019-08-20 | Eden Research Plc | Preservatives |
| US10667512B2 (en) | 2005-11-30 | 2020-06-02 | Eden Research Plc | Terpene-containing compositions and methods of making and using them |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE28263E (en) * | 1962-03-14 | 1974-12-03 | Disinfecting compositions |
-
1990
- 1990-03-09 US US07/491,459 patent/US5068453A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE28263E (en) * | 1962-03-14 | 1974-12-03 | Disinfecting compositions |
Non-Patent Citations (4)
| Title |
|---|
| Larcheveque et al., Tet. Lett., 22(17), 1595 8 (1981). * |
| Larcheveque et al., Tet. Lett., 22(17), 1595-8 (1981). |
| Poulter et al. (1981) Journal of Organic Chemistry, 46:1532 1538. * |
| Poulter et al. (1981) Journal of Organic Chemistry, 46:1532-1538. |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6623724B2 (en) | 1996-09-18 | 2003-09-23 | Applied Genetics Incorporated Dermatics | Dermatological compositions and methods |
| US20040067209A1 (en) * | 1996-09-18 | 2004-04-08 | Applied Genetics Incorporated Dermatics | Dermatological compositions and methods |
| US6955804B2 (en) | 1996-09-18 | 2005-10-18 | Applied Genetics Incorporated Dematics | Dermatological compositions and methods |
| US20060120976A1 (en) * | 1996-09-18 | 2006-06-08 | Applied Genetics Incorporated Dermatics | Dermatological compositions and methods |
| US7250157B2 (en) | 1996-09-18 | 2007-07-31 | Applied Genetics Incorporated Dermatics | Dermatological compositions and methods |
| US6214888B1 (en) | 1996-09-18 | 2001-04-10 | Applied Genetics Incorporated | Dermatological compounds |
| EP1420640A4 (en) * | 2001-08-28 | 2004-11-24 | Eden Research Plc | Treatment and prevention of infections in plants |
| US20040248764A1 (en) * | 2001-08-28 | 2004-12-09 | Franklin Lanny U | Treatment and prevention of infections in plants |
| US7741037B2 (en) | 2002-04-30 | 2010-06-22 | Board Of Regents, The University Of Texas System | Method for pheromone discovery in insects |
| US20060127944A1 (en) * | 2002-04-30 | 2006-06-15 | Renthal Robert D | Method for pheromone discovery in insects |
| US7074572B2 (en) | 2002-04-30 | 2006-07-11 | Board Of Regents, The University Of Texas System | Method for pheromone discovery in insects |
| US20080220038A1 (en) * | 2004-01-23 | 2008-09-11 | Lanny Franklin | Nematicidal Compositions and Methods of Using Them |
| US9655360B2 (en) | 2004-01-23 | 2017-05-23 | Eden Research Plc | Nematicidal compositions and methods of using them |
| US10004229B2 (en) | 2004-01-23 | 2018-06-26 | Eden Research Plc | Nematicidal compositions and methods of using them |
| US10729130B2 (en) | 2004-01-23 | 2020-08-04 | Eden Research Plc | Nematicidal compositions and methods of using them |
| US20100040656A1 (en) * | 2004-05-20 | 2010-02-18 | Lanny Franklin | Compositions containing a hollow glucan particle or a cell wall particle encapsulating a terpene component, methods of making and using them |
| US10638750B2 (en) | 2004-05-20 | 2020-05-05 | Eden Research Plc | Compositions containing a hollow glucan particle or a cell wall particle encapsulating a terpene component, methods of making and using them |
| US9439416B2 (en) | 2005-11-30 | 2016-09-13 | Eden Research Plc | Compositions and methods comprising terpenes or terpene mixtures selected from thymol, eugenol, geraniol, citral, and l-carvone |
| US10258033B2 (en) | 2005-11-30 | 2019-04-16 | Eden Research Plc | Compositions and methods comprising terpenes or terpene mixtures selected from thymol, eugenol, geraniol, citral and L-carvone |
| US10667512B2 (en) | 2005-11-30 | 2020-06-02 | Eden Research Plc | Terpene-containing compositions and methods of making and using them |
| US10383329B2 (en) | 2012-11-21 | 2019-08-20 | Eden Research Plc | Preservatives |
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